Floor polish composition having improved initial water and detergent resistance

ABSTRACT

An improved aqueous polymer-emulsion floor polish composition containing an aqueous mixture of a wax, an alkali soluble resin, a polymer emulsion, and both a calcium compound dissociable in the composition to form Ca 2 ions and a zinc compound dissociable in the composition to form Zn 2 ions. These compositions exhibit initial water resistance when applied to a floor as a coating and dried.

' 22 Filed:

United States Patent 1191 Oliver et al. 1 I

[541 FLO RPoLIsII COMPOSITION HAVING IMPROVED INITIAL WATER ANDDETERGENT RESISTANCE [75 Inventors Connie J. Oliver; Edward We,

both of Pittsburgh, Pa. 15219 [73] Assignee: Sinclair-Koppers Co.

' March 2, 1971 [21 Appl. NO.: 120,321

[52] US. Cl. ..260/28.5 R, 260/29.6 RB [51] Int. Cl. ..C08i 45/52, C08f45/24 [58] FieldofSearch....' .206/28.5R

15 References Cited V UNITED STATES PATENTS- 3,403,119 9/1968 Sullivanem. ..260/28.5R

3,457,208 7/1969 SullivanetaL; ...260/28.5R

3,467,610 3,554,790 1/1971 Gehman et al 260/285 R 3,573,239

' 3/197] Zclanowski et al .:260/28.5 R

Primary Examiner-Morris Liebman Assistant Examiner-S. C. Fox

Attorney Lewis J. -Young, Oscar B. Brumback and Olin E. Williams i 57ABSTRACT An improved aqueous polymer-emulsion floor polish compositioncontaining an aqueous mixture of a wax,

7 Claims, No Drawings 9/1969 Fiarman etal ..260/2 8.5 R

FLOOR POLISH COMPOSITION HAVING IMPROVED INITIAL WATER AND DETERGENTRESISTANCE BACKGROUND OF THE INVENTION This invention relates to coatingcompositions and especially to floor polishing compositions which areparticularly suitable for applying glossy finishes 'on wood, rubber,glass, tile, linoleum and the like surfaces.

More particularly, this invention relates to such coating compositionshaving improved initial water and detergent resistance.

Many types of floor polish compositions are known which can be appliedto floors to provide, upon drying,

- a protective coating to the floor. Emulsion floor polish compositionsusually include as principal ingredients a water-insoluble emulsionpolymer or latex to provide toughness, high gloss, and durability to thecoating, and a mixture of a wax and an alkali soluble resin to provide afilm forming matrix for the emulsion polymer. The balance of the polishusually includes emulsifying agents, dispersing agents, plasticizers,water and other special purpose additives.

Floor polish compositions to be useful must be capable of being readilyremoved from the floor when they become dirty or marred after extendeduse. Aqueous alkaline mediums such as aqueous' ammonia solutions areusually effective in removing polish compositions containing alkalisolubleresins. In addition to being readily removable in 'an aqueousalkaline medium, floor polishes must be able to resist being damaged bywater or water based detergents. Water is frequently spilled on floorsand thus any floor coating must have good water resistance. Further,although after extended use floor coatings need to be removed andreplaced with a fresh coating, they preferably are formulated so thatthey can be washed free of dirt with water based detergents, andmustthus possess good detergent resistance. Floor polish compositionswhich possess both good removability and good water resistance aredifficult to formulate.

Freshly applied floor polishes are often subject to damage by water inthe first 24 hours after the polish dries. After 24 hours dried polishfilms generally have good water spot resistance. Drops of water whichfall on a freshly polished floor cause objectionable white spots toappear in the dry but new film. Therefore, floor polish additives whichcause a floor polish to become water resistant in a short period of timeare desired. There are very few known compounds, however, that arecapable of making floor polishes resistant to the damaging effects ofwater soon after application.

One such water resistant floor polish composition contains a polyvalentmetal compound that forms a metal complex with the resins andemulsion-polymer in the composition. The metal compound dissociates inthe polish to form polyvalent metal ions which then form the complex.Polishes which have been so complexed with metals are generally moreresistant to destruction by water and detergent solutions than floorpolish compositions which have not been, and thus can be washed morefrequently with water based detergents. The most useful of these metalcompounds are those that not only form metal complexes but which arealso readily solubilized by ammonia for easy removal.

In the past, polishes have been complexed with either zinc alone or withcalcium alone to form water resistant floor polishes. One disadvantageof these polish compositions is that the dried floor coatings do notdevelop initial water resistance,- that is, they do not possess a goodlevel of water resistance until after at least about 48 hours. Initialwater resistance of these compositions has been improved somewhat bycuring the floor polish at C for an extended period of time before it isapplied to the floor, but this is not a practical method of achievinginitial water resistance.

Summary of the Invention In accordance with the present invention, ithas been found that a floor polish composition having improved initialwater resistant properties, can be provided comprising an aqueousmixture of emulsion-polymer, wax, and alkali soluble resin, and both acalcium compound dissociated in the mixture to form Ca ions and a zinccompound dissociated in the mixture to form Zn ions.

Detailed Description of the Invention Surprisingly, it has been foundthat a floor polish composition containing both a calcium complexingcompound as well as a zinc complexing compound produces a fioor coatinghaving an initial water resistance substantially greater than floorcoatings produced from floor polish compositions having solely a calciumor a zinc complexing compound. In fact, the floor compositions of thepresent invention exhibit good water resistance after only about 24hours from drying which prevents up to and including percent of thecomposition from being removed or damaged by water, whereas compositionsthat contain either solely calcium ions or solely zinc ions are almostcompletely removed and damaged by water during this same period.

Preferably, based on the weight of resin and emulsion-polymer, the zinccompound comprises from about 0.6 to 6.0 percent by weight of thecomposition and the calcium compound comprises from about 0.4 to 4.0%by' weight of the composition. It is also preferred that themolar ratioof Zn ions to Ca ions be between about 1 4 and 4 l. The emulsion-polymeris preferably a styrene-butyl acrylate copolymer or a special blend of astyrene copolymer with a styrene multipolymer. The alkali-soluble resinis preferably a styrene-maleic anhydride copolymer.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory but arenot restrictive of the invention.

In accordance with the invention, the floor polish compositions comprisean aqueous mixture which contains a polyvalent zinc compound and apolyvalent calcium compound both dissociable in the mixture. The amountof each metal compound in the composition can be from 0.4 to 6.0 percentand is preferably about 1.0 to 3.0 percent by weight, based on theweight of alkali soluble resin and emulsion polymer in the composition.The weight of each specific calcium and zinc compound needed to providean equivalent amount of ions in the composition, of course, varies withthe molecular weight of the compound. To impart improved initial waterand detergent resistance to the floor polish'comstyrene-butyl positionswithout deleteriously affecting its other properties, the compositionshould contain 0.1 to 2.5 millimoles of Ca ions per 100 grams of polish,and 0.1 to 2.5 millimoles of Zn ions per 100 grams of polish.Preferably, 0.5 to 1.5 millimoles of Ca per 100 grams of polish and 0.5to 1.5 millimoles of Zn ions per 100 grams of polish are provided in thecomposition. A l 1 molar ratio of Zn ions to Ca ions is generallypreferred in the polish composition.

Generally, suitable zinc and calcium compounds that can be used in thecomposition to provide zinc and calcium ions which form metal complexeswithin the polish compositions are the oxides, hydroxides, or otherbasic, acidic, or neutral salts of zinc and calcium. Zinc and calciumcompounds which have appreciable solubility in water, such as, at least1 percent by weight therein, are most useful.

The ammonia and amine complexes of zinc, and especially those containingcoordinated NH are particularly useful as the zinc compound. Presently,it is preferred to use the zinc-ammonia complex Zn(NH) o asthe zinccompound for providing the zinc ions in the floor polish composition.Exemplary of other zinc compounds that can be used are ZnCO ZnO, and Zn(OH It is also preferred to use calcium carbonate as the calcium,compound which provides the calcium ions in the floor polishcomposition. Exemplary of other specific calcium compounds that can beused are calcium hydroxide, and calcium oxide.

In accordance with the invention, the floor polish compositions containan aqueous polymer emulsion or latex. The term polymer emulsion isintended to include'copolymers as well. The latices are derived fromethylenically unsaturated monomers and include emulsions containingpolystyrene, polyvinyl chloride and polyacrylic resins, aswell as blendsof polystyrenepoly acrylic resins, and complex styrene-acryliccopolymers.

When used in the floor polish composition, the aqueous polymer emulsionusually contains to 20 percent polymer, based on the weight of thepolymer emulsion.

The polymer or solids-content of the aqueous emulsion polymer usuallycomprises 50 to 80 percent by weight of the total solids present in thepolish compositions and normally is the major solid constituent presentin the polish composition.

Generally, the total solids content of the floor polish compositionranges from about. 5 to about30 percent by weight of the composition.The preferred total solids content of the polish for producing ease ofapplication is from about 10 to about 20 percent. The remainder of thecomposition is generally aqueous and usually is water.

Preferably, the latex portion of the floor polish composition is eithera low pH styrene-butyl acrylate copolymer or a blend of specific styrenepolymers. The acrylate copolymers are emulsion polymers comprised of 30to 50 percent styrene, 20 to 55 percent butyl acrylate, and to 30percent of ethylenically unsaturated monomers such as methacrylic acidand acrylonitrile. A-particularly useful styrene-butyl acrylatecopolymer is a copolymer prepared from styrene, butyl acrylate,methacrylic acid and acrylonitrile in the ratio of 38:37:l0:l5 parts byweight,-which can be prepared by conventional sion polymerizationtechniques.

The preferred blend of styrene polymers consists essentially of 50 topercent by weight of a styrene copolymer, and 50 to 20 percent by weightofa styrene mul'ti-polymer.

The styrene copolymer of the preferred blend is an emulsion polymercomprised of percent styrene and 10 5 percent of an ethylenicallyunsaturated monocarboxylic acid selected from acrylic and methacrylicacid. This copolymer is generally termed a hard polymer because of itsbrittle properties and although forming a tough film, is subject tocrazing or cracking if used alone in floor polishes. When employed inpolishes, significant amounts of plasticizers are needed to reduce thebrittle character of this copolymer.

The specially prepared styrene emulsion multipolymer of the blendconsists of a polymer formed from l0 40% styrene and 90 60 percent ofamixture of ethylenically unsaturated monomers. The ethylenicallyunsaturated monomers are all of the general formula:

(l l Jl-li.

wherein R is COOH; or R is COOR wherein R is an alkyl group having l-8carbon atoms; or R is C N; and R is selected from hydrogen anda methylgroup.

Preferably, the mixture of ethylenically unsaturated monomers used toform the. multi-polymer has certain percentages of the variousethylenically. unsaturated monomers. Thus, the mixture of ethylenicallyunsaturated monomers used to form the multi-polymer contains, based onthe multi-polymer, from I to 10% by weight of the ethylenicallyunsaturated monomer wherein R is COOH, such as acrylic acid ormethacrylic acid. From about 30 80 percent of the mixture is anethylenically unsaturated monomer wherein R is CO OR with R being analkyl group of from one to eight carbon atoms, such as ethyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, ethyl methacrylate and the like.The remaining monomer, acrylonitrile, or methacrylonitrile is present inabout 5-25 percent. A blend containing the described styrenemultipolymer exhibits a resistance to plasticizer migration from theflooring into the floor polish coating.

The emulsion polymers useful in the present invention are readilyprepared from the-desired monomers by conventional aqueous emulsionpolymerization procedures. Preferably, the monomers are premixed,

the catalyst is premixed-to form an aqueous solution or slurry and thesetwo premixes added to. an aqueous.

charge in a reactor. The catalyst premix comprises water, catalyst,dispersants, and emulsifying agents.

.Conve ntional polymerization catalysts or mixtures thereof includingpotassium persulfate, benzoyl peroxide, azobisisobutyronitrile and thelike. The catalysts are generally used in about 0.01 1.0 part per partsby weight of total monomers.

Conventional emulsifying agents such as alkali metal salts of long chainalkyl sulfates and sulfonates, ethylene oxide condensates of long chainfatty acids, alcohols or mercaptans, sodium salts of sulfonatedhydrocarbons, alkyl arylsulfonates and the like are usable.Representative emulsifying agents include such compounds as' sodiumlauryl sulfate, sulfosuccinate acid esters, sodium salts of bioctylsulfosuccinate acid,

hydroxide, n'ionoethanolamine, and the like. When forming the preferredstyrene-butyl acrylate copolymer the polymerization is carried out underacidic conditions and the aqueous emulsion polymer pH raised to a pH ofabout 8.0 to 9.0, following the polymerization with inorganic or organicbases such as ammonia, 3- methoxy-N-propylamine, and morpholine. Thewater content of the aqueous polymerization system is generally suchthat between about 30-55 percent solids are present during thepolymerization, with the amount increased or decreased as desired.

In accordance with the invention, the floor polish compositions of thepresent invention usually contain alkali-soluble resins. Examples ofsuitable alkali-soluble resins are rosin acid, maleate-modified rosinacid ester, shellac, styrene-maleic anhydride copolymers, polyesters oralkali soluble alkyds, peritaerythritol ester of rosin, manilla gum,Loba gum and the like. The alkali soluble resins are usually added tothe floor polish composition as an aqueous emulsion containing -20percent resin based on the weight of the emulsion. The resin usuallycomprises 10 to 30 percent by weight of the total solids present in thepolish composition.

Preferred alkali-soluble resins for use in the present invention arestyrene-maleic anhydride copolymers which contain styrene copolymerizedwith maleic anhydride in a molar ratio between about 1:1 and about 3:1.These materials are commercially, available. The materials, whichcontain acid anhydride groups, have a molecular weight between about 700and about 2,500, usually between about 1,600 and about 2,200, andcontain on the average about 8 repeating units each comprising a maleicanhydride group and one, two, or three styrene molecules in conjunctiontherewith. For example, one such copolymer has a molecular weight of1,900 and an acid number of 275. These polymeric vacid anhydridematerialsare solids whose melting points vary from about 140C to about180C, and are water-insoluble materials.

In accordance with the present invention, the floor polish compositionscontain a waxy material. Suitable wax'es, which are generally added asabout a 10-20 percent by weight aqueous emulsion, are the animal,vegetable and synthetic waxes such as carnauba. polyethylene,polypropylene, oxidized microcrystalline paraffin wax, beeswax, montan,and the like. For addian AC-629 polyethylene, a well known low molecularweight polyethylene wax having a melting point of 2l3-221F andmanufactured by the Allied Chemical Corporation, New York, New York. V I

In addition, optional minor ingredients conventionally used in floorpolish compositions can be incorporated in the compositions of thepresent invention. Exemplary of the optional ingredients that can beadded are leveling or coalescing agents. Leveling or coalescing agentsusually comprise about 0.5-1 percent by weight of the total polish andinclude tributoxyethyl phosphate, triethyl phosphate, tributylphosphate, tricresyl phosphate, triphenyl phosphate, diethylene' glycolmonomethyl ether, diethylene glycol monoethyl ether and the like.

To form the polish compositions of the present invention, the emulsionpolymer, plasticizers, dispersing agents or coalescing agents, otheroptional ingredients, the alkali soluble resin in aqueous emulsion form,and the wax in aqueous emulsion form are all mixed together. The polymeremulsion, wax emulsion and altion to floor polish. compositions, thesewaxes are dispersed in water with surface active agents such as sorbitolcondensate adducts, polyglycol ether products, alkali or amine salts offatty acids, sulfates, and sulfonates. The waxes usually comprise 5 to20 percent by.

weight of the total solids present in the polish composition.

. Preferred waxes for use in the present invention are polyethylenewaxes. A typical polyethylene wax emulsion can be formed at a 13 percentsolids content from kali soluble resin emulsion can be mixed in anyorder desired. The polymer emulsion is usually preplasticized withplasticizing agents such as tributoxyethyl phosphate, dibutyl phthalateand diethylene glycol monomethyl ether. Preferably, the resin is addedto the preplasticized polymer emulsion, followed by addition of the waxemulsion, and optional minor ingredients such as leveling-agents. Thepolish is then usually mixed for a minimum period of two hours toachieve the final polish blend.

The polyvalent metal compounds used in the present invention can beincorporated into the composition at any time. Preferably, however, the.zinc compound is added to the composition after the emulsion polymer andresin have been mixedtogether, but before the addition of the wax. Thecalcium compound is preferably added to the emulsion polymer and mixedinto the latex portion for several hours until a uniform appearance isobtained before the emulsion polymer is preplasticized. The metalcompounds are usually added in incremental amounts to aid theirsolvation in the composition.

For a clearer understanding of the invention, specific examples of itare set forth below. These examples are merely illustrative of thisinvention and are not to be understood aslimiting the scope andunderlying principles of the invention in any way. All percentages andparts referred to herein are by weight unless otherwise specificallyindicated.

EXAMPLE I Styrene 14 parts Ethyl Acrylate 65 parts Acrylonitrile 20parts Acrylic Acid 1 part 15.5 .parts' of a water soluble styrene-maleicanhydride copolymer resin sold under the trade name SMA 3,000A availablefrom Texas Butadiene and Chemical Corporation; 11.5 parts of apolyethylene wax emulsion (AC-629, a low molecular weight polyethylenewax, mp. 21 3-22lF, 13 percent solids); 0.8 parts of tributoxyethylphosphate, 1.5 diethylene glycol monomethyl ether, and 0.3 partsdibu'tyl phthalate as plasticizer; 1.0 parts FC-l28, at, 1 percentsolids, as a leveling aid, available from Minnesota Mining andManufacturing Company; and 0.8 parts Igepal CO-990, at percent solids,as a leveling aid, available from General Aniline and Film Corp. I

The polish composition has a total solids content of 13.0 percent and apH of 8.5.

Also incorporated in this floor polish composition in accordance withthe invention is 0.10 parts of CaCO as the calcium compound, and 0.18parts of the zinc ammonia complex Zn(NI-I CO as the zinc compound. TheCaCO is added to a mixture of emulsion A with emulsion B, and theZn(NI-I CO:, is added to the composition after plasticizers and resinare admixed with the emulsion polymer mixture.

EXAMPLE II The floor polish composition of Example I (Composition I)containing both the zinc compound and the were tested for initialdetergent resistance and remova-- bility.

An 0.8 c.c. sample of each of the floor polish com-- positions isapplied to a 9 inch X 9 inch solid vinyl tile and spread over a 2 inch X8 inch area via a doctor blade set at 0.008 inch. The tile is thenscrubbed with a Gardner scrub machine with a brush that is covered witha cheesecloth pad that has been soakedfor one minute in 10 mls. of Spicand Span. The test is run.24

TABLEI EVALUATION OF INITIAL DETERGENT RESISTANCE AFTER 24 HOURS ON TILEPercent of film removed Metal Compounds Composition no. in composition lZn and Ca very little 2 Zn all 3 Ca substantially all As seen from TableI, Composition No. I of Example I which is prepared in accordance withthe teachings of the present invention is barely removed, whereas thecompositions containing calcium compounds or zinc compounds solely aresubstantially completely removed by the scrub test. Thus, compositionscontaining an addition of both calcium compounds and zinc compoundsprovide improved initial detergent resistance.

To further test the compositions for their initial detergent resistance,each of the above three floor polish compositions are placed in a glassbottle which is then capped and stored in an electric oven maintained atC. The compositions are cured in the oven for 24 hours, removed, andthen tested for initial detergent resistance in an identical manner asthat used above. The results of this test are set forth in Table IIbelow.

TABLE II EVALUATION OF INITIAL DETERGENT RESISTANCE OF CURED POLISH COMPOSITIONS AFTER 24 HOURS ON TILE Composition No. Metal compounds Percentof film As can be seen from a comparison of Tables I .and II, curing thefloor polish compositions markedly increases the initial detergentresistance of compositions having solely a zinc compound or solely acalcium compound added thereto, whereas curing brings about only a smallincrease in the compositionhaving both a calcium and zinc compound addedthereto. Importantly, the uncured composition of the present inventionhas. a greater initial detergent resistance than cured compositionsnotcontaining both the. calcium and zinc addition of the present invention.

The cured and uncured floor polish compositions are also tested todetermine'their removability. The same procedure and apparatus that wereused to determine initial detergent resistance is used for determiningremovability except that the Spic and Span solution is ammoniated. I v

The removability test is conducted 24 hours after the polishes areapplied to the tile. The results of the removability test after50'cycles of scrubbing are set forth in Table III below.

TABLE III EVALUATION OF REMOVABILITY OF POLISH COMPOSITIONS AFTER 24HOURS ON TILE Metal compound Percent of film Composition No. inComposition Removed l (uncured) Zn and Ca all 1 (cured) Zn and Casubstantially Y 2 (uncured) Zn all 2 (cured) Zn all 3 (uncured) Ca all 3(cured) Ca all EXAMPLE III In this example a floor polish composition ismade according to the teachings of the present invention in a manneridentical to Example I except that the blend of styrene copolymer andstyrene multipolymer as the latex portion of the floor polish isreplaced by 73 parts of a styrene, butyl acrylate, methacrylic acid,acrylonitrile copolymer having a weight ratio of 38:37:10215,respectively. The zinc and calcium compounds are added as described inExample I.

EXAMPLE IV The floor polish composition of Example lll (Composition 4)is compared to two floor polish-compositions that were prepared in anidentical manner to the composition of Example lll except that one ofthese compositions (Composition 5) had only the zinc compound added toit, and the other floor polish compositions (Composition 6) had only thecalcium compound added to it. The initial detergent resistance andremovability tests of Example." were run on uncured and cured samples ofComposition Nos. 4, 5, and 6. The results of these tests .are set forthin Table lV below.

TABLE Iv EVALUATION OF INITIAL DETERGENT 6 (cured) resistance, while theuncured compositions containing only one of these metal compoundsexhibit practically no initial detergent resistance. v p

The invention in its broader aspects is not limited to the specificdetails shown and described and departures may be made from such detailswithout departing from the principles of the invention and withoutsacrificing its chief advantages.

What is claimed is: 1. An improved aqueous polymer-emulsion floor polishcomposition comprising, in combination, an aqueous mixture of:

a. 5-20 percent by weight based on total solids of a wax; b. 10-30percent by weight based on total solidsof an alkali-soluble resin; c.50-80 percent by weight based on total solids of an emulsion polymercomprising a blend of styrene polymers consisting of an admixture of:

1. 50-80 percent by weight of a styrene copolymer consisting of -95percent byweight of the copolymer of styrene and 540% byweight of anethylenically unsaturated monocarboxylic acid selected from acrylic andmethacrylic acid; and

50-20 percent by weight of a styrene -multipolymer consisting of l0-40percent by weight of styrene and 90-60 percent by weight of a mixture ofethylenically unsaturated monomers of the formula: I

wherein R is -COOH; -COOR wherein R is an alkyl group having l-8 carbonatoms; or C E N, and

, R, is hydrogen or methyl, said styrene multi-polymer containing fromll0 percent by weight of said monomer wherein R is COOH, 30-80 percentof said monomer wherein R is -COOR and 5-25 percent of said monomerwherein R is C i N;

d. 0.4 4.0 percent by weight based on the weight of resin and emulsionpolymer of a calcium compound dissociated in. the mixture to form Caions; and I e. 0.6 6.0 percent by weight based on'the weight of resinand emulsion polymer of a zinc compound dissociated in the mixtureto'form Zn ions; said calcium and zinc compounds being present inamounts such that the molar ratio Zn to Ca ions is between 1:4 and 4:1and said composition having a total solids content of between 5 and 30percent by weight of total mixture.

2. The composition of Claim 1 wherein the molar acid, acrylonitrile, andmethacrylonitrile.

6. The composition of claim 4 wherein the styrene- LII v 12 butylacrylate cop'olymerconsists of 38 percent styrene, 37 percent butylacrylate, 10 percent methacrylic acid, and 15 percent acrylonitrile.

7; The composition of claim 1 'wherein the alkali soluble resin is astyrene-maleic anhydride copolymer.

2. The composition of Claim 1 wherein the molar ratio of Zn 2 ions to Ca2 ions is about 1:1.
 2. 50-20 percent by weight of a styrenemulti-polymer consisting of 10-40 percent by weight of styrene and 90-60percent by weight of a mixture of ethylenically unsaturated monomers ofthe formula: wherein R is -COOH; -COOR2, wherein R2 is an alkyl grouphaving 1-8 carbon atoms; or -C*N, and R1 is hydrogen or methyl, saidstyrene multi-polymer containing from 1-10 percent by weight of saidmonomer wherein R is -COOH, 30-80 percent of said monomer wherein R is-COOR2, and 5-25 percent of said monomer wherein R is -C*N; d. 0.4 - 4.0percent by weight based on the weight of resin and emulsion polymer of acalcium compound dissociated in the mixture to form Ca 2 ions; and e.0.6 - 6.0 percent by weight based on the weight of resin and emulsionpolymer of a zinc compound dissociated in the mixture to form Zn 2 ions;said calcium and zinc compounds being present in amounts such that themolar ratio Zn 2 to Ca 2 ions is between 1:4 and 4:1 and saidcomposition having a total solids content of between 5 and 30 percent byweight of total mixture.
 3. The composition of claim 1 wherein the saidcopolymer consists of about 95 percent styrene and about 5 percentacrylic acid, and said multipolymer consists of about 14 percentstyrene, about 65 percent ethyl acrylate, about 1 percent acrylic acid,and about 20 percent acrylonitrile.
 4. The composition of claim 1wherein the emulsion polymer comprises a styrene-butyl acrylatecopolymer.
 5. The composition of claim 4 wherein the styrene-butylacrylate copolymer comprises 30 to 50 percent styrene, 20 to 55 percentbutyl acrylate, and 15 to 30 percent ethylenically unsaturated monomersselected from the group consisting of acrylic acid, methacrylic acid,acrylonitrile, and methacrylonitrile.
 6. The composition of claim 4wherein the styrene-butyl acrylate copolymer consists of 38 percentstyrene, 37 percent butyl acrylate, 10 percent methacrylic acid, and 15percent acrylonitrile.
 7. The composition of claim 1 wherein the alkalisoluble resin is a styrene-maleic anhydride copolymer.